CN101518718A - 一种烟气有害成分净化用功能性过滤毡及其制备、应用方法 - Google Patents
一种烟气有害成分净化用功能性过滤毡及其制备、应用方法 Download PDFInfo
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- CN101518718A CN101518718A CN200810101151A CN200810101151A CN101518718A CN 101518718 A CN101518718 A CN 101518718A CN 200810101151 A CN200810101151 A CN 200810101151A CN 200810101151 A CN200810101151 A CN 200810101151A CN 101518718 A CN101518718 A CN 101518718A
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- Prior art keywords
- filter felt
- fibrous material
- catalyst
- fume
- functional
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- 239000003517 fume Substances 0.000 title claims abstract description 26
- 239000000470 constituent Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 122
- 239000002657 fibrous material Substances 0.000 claims abstract description 83
- 230000003009 desulfurizing Effects 0.000 claims abstract description 43
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 37
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitrogen oxide Substances 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O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000000428 dust Substances 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 229910052813 nitrogen oxide Inorganic materials 0.000 claims abstract description 13
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- 230000004048 modification Effects 0.000 claims abstract description 6
- 238000006011 modification reaction Methods 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 239000010410 layer Substances 0.000 claims description 67
- 239000000835 fiber Substances 0.000 claims description 65
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 63
- 229920000069 poly(p-phenylene sulfide) Polymers 0.000 claims description 63
- 239000003546 flue gas Substances 0.000 claims description 61
- UGFAIRIUMAVXCW-UHFFFAOYSA-N carbon monoxide Chemical compound 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[O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 59
- 239000000463 material Substances 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000002131 composite material Substances 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound 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[C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 239000000969 carrier Substances 0.000 claims description 21
- 230000003197 catalytic Effects 0.000 claims description 19
- QPLDLSVMHZLSFG-UHFFFAOYSA-N copper oxide Chemical compound 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- 238000002156 mixing Methods 0.000 claims description 15
- 206010052769 Vertigos Diseases 0.000 claims description 13
- 239000003365 glass fiber Substances 0.000 claims description 13
- GEIAQOFPUVMAGM-UHFFFAOYSA-N oxozirconium Chemical compound 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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group data:image/svg+xml;base64,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 data:image/svg+xml;base64,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 [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
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- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims description 10
- 150000004706 metal oxides Chemical class 0.000 claims description 10
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- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials 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[Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- 239000011152 fibreglass Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound 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[Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 239000011229 interlayer Substances 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium Chemical compound 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[Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials 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- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
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[Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
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- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulphur dioxide Chemical compound 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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound 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O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
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- 229910002089 NOx Inorganic materials 0.000 description 2
- CVTZKFWZDBJAHE-UHFFFAOYSA-N [N].N Chemical compound 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[N].N CVTZKFWZDBJAHE-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive Effects 0.000 description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound 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- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound 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[S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
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Abstract
本发明属于烟气净化技术领域,所提供的烟气有害成分净化用功能性过滤毡在除尘的同时,能够实现烟气的脱硫或脱硝,或者同时脱硫脱硝。该过滤毡由纤维材料和功能催化剂复合制成,在烟气有害成分净化过程中,通过耐高温纤维材料制造的非织造布过滤烟气中的粉尘,以过滤毡中含有的功能催化剂实现催化反应脱除烟气中的氮氧化物(NOX)和/或硫氧化物(SOX)。所提供的过滤毡适用于电厂、炼厂、化工厂的烟气除尘、脱硫和脱硝装置,特别适用于制造烟气袋式过滤器。与现有技术比较,本发明简化了烟气净化工序,提高处理效率,并有效地节省投资和降低运营费用,非常适合对现有的烟气除尘装置进行改造。
Description
一种烟气有害成分净化用功能性过滤毡及其制备、应用方法技术领域本发明涉及烟气净化技术领域,所提供的烟气有害成分净化用功能性过滤毡及 其应用方法在除尘的同时,实现烟气的脱硫或脱硝,或者同时脱硫脱硝。 背景技术工业烟气中含有大量的对环境和人类有害的物质如粉尘、硫氧化物(S0x)和氮 氧化物(N0x), 一旦排入大气将成为主要的空气污染源和光化学污染源。随着我国 环保法规的日益严格,控制粉尘、硫氧化物和氮氧化物污染物的排放对我国国民经 济可持续发展具有极其重要的意义。现有专利中,中国公开专利CN1451462A提供一种烟气有害成分的净化方法和装 置,其特点是采用袋式除尘器净化单元实现烟气除尘和吸附脱除微量重金属和有机 污染物等成分。但上述已有的技术,在除尘的同时对烟气中大量有害的硫氧化物、氮氧化物的 去除能力有限,必须与其它现有烟气脱硫、脱硝技术结合才能够有效地减少硫氧化 物(S0x)、氮氧化物(N0x)排入大气,如申请号为200610012526的中国专利,提供 了一种烟气光催化氧化同时脱硫脱硝的方法及装置,其技术方案是:将燃煤烟气引 入反应器内,在反应器内充填光催化剂,并用光照射催化氧化,所述光催化剂由载 体、0.5%质量比的二氧化钛和添加剂组成,所述载体为石英砂,其粒径为4〜6mm, 所述光催化剂为二氧化钛和添加剂的混合物。该发明可以同时完成脱硫和脱硝;申 请号为99104245的中国专利,提供了一种烟气脱硫催化剂及其应用方法,催化剂各 组分的重量百分比为"炭材料80—95%,铜5_20%,炭材料载体包括活性炭、活性 焦或活性炭纤维。用于工业锅炉烟气脱硫,将催化剂装入固定床反应器中,反应温 度控制在120—300。C,通入常压烟气,空速为500 — 80000h、Ar为平衡气。申请号为 200610044991.9的中国专利,提供了一种高尘复合SCR烟气脱硝工艺,将含有NOx的 烟气经可控阻流装置进圆盘环形氨气喷射格栅并与通过圆盘环形氨气喷射格栅喷嘴 喷出的氨气混合,经双螺旋混合装置使氨氮气体在湍流和螺旋板的共同作用下,充 分而均匀混合,然后经氨氮混合气导流板进入设有超声波振动除尘装置的催化剂反 应器上部气室,而后再向下进入金属氧化催化剂层中还原成N2和H20,由催化剂反应器出来的经脱硝后的烟气通过热交换、除尘和脱硫,最后从烟囱排出,吸附在催化剂表面的灰尘在超声波振动除尘装置的作用下落入催化剂反应器底部的灰斗中,待排。
以上工艺都是将除尘和脱硫和/或脱硝分为两个步骤,在不同的装置中实现,随之带来了烟气净化装置投资大、工艺复杂、操作繁琐和运行成本大的缺点,而且除尘和脱硫和/或脱硝难以协调进行。申请号为01144578的中国专利提供了一种烟气除尘脱硫一体化的方法和装置,使用混合造粒器将催化剂、脱硫剂和持水剂混合造粒形成复合颗粒,并用高温蒸汽增湿活化后随烟气一起进入袋式除尘器,复合颗粒通过在烟气、预反应仓的反应和吸附,最后进入袋式除尘器;使滤料表面形成颗粒层,并再次对二氧化硫和细颗粒进行脱除和吸附反应,将滤料表面脱落并自行进入灰仓的粉尘回送至循环灰仓,使循环灰仓和混合造粒器通过控制系统实现交替运行,实现复合颗粒的循环使用,可应用于烟气和二氧化硫的同时脱落。但该工艺仍然显复杂,催化剂消耗量过大,而且催化剂需要经过袋式除尘器的吸附在滤料表面形成颗粒层,必然造成催化剂分布的不均衡,造成了脱硫反应的不均衡,弱化了脱硫效果。
此外,中国授权专利CN2669958Y提供了一种耐高温吸附过滤毡,是由玻璃纤维、聚苯硫醚(PPS)纤维和活性碳纤维复合、经过PTFE化学处理的针刺过滤材料,具有除尘和脱除气体中的含酸腐蚀性气体(主要指S02)的功能。但是其脱除原理是通过活性炭纤维的吸附作用,因此存在脱硫深度不够,活性炭的硫容量较低,使用周期短,且再生性能不好等问题,大大限制了其工业应用。
有鉴于此,特提出本发明,所提供的烟气有害成分净化用功能性过滤毡,是集除尘、脱硫和/或脱氮一体化的功能材料,可以减少烟气净化处理工序,简化了烟气净化工序,提高处理效率,可以有效地节约费用,非常适合对现有的烟气除尘装置进行改造。
发明内容
本发明的目的在于提供一种烟气有害成分净化用功能性过滤毡。
本发明的另一目的在于提供上述过滤毡的制备方法。
本发明的另一目的在于提供上述过滤毡的应用方法。
本发明提供的一种烟气有害成分净化用功能性过滤毡,其特征在于,所述的过
5滤毡由纤维材料和具有催化脱硫和/或脱氮反应的功能性催化剂组成。
其中,所述功能性催化剂以粘接、附着或通过湿、热、挤压等物理作用或化学
反应与纤维材料复合。
所述的纤维材料至少为一层,所述的功能性催化剂为单独的一层或分散在纤维
材料中。
所述的过滤毡由两层纤维材料层和一层功能性催化剂层构成,功能性催化剂层置于两层纤维材料层之间,
或所述的过滤毡由两层纤维材料层和功能性催化剂构成,功能性催化剂分散在纤维材料层中,
或所述的过滤毡由一层纤维材料层和一层功能性催化剂层构成。
所述的纤维材料具备耐高温特性。
所述的纤维材料为
a、 聚苯硫醚、经过等离子体表面改性的聚苯硫醚、芳纶、玻璃纤维中的一种或
两种以上复合纺丝或混纺所得的纤维,或
b、 将a中的纤维与其它纤维材料的复合纺丝或混纺所得的纤维^或
c、 将a或b中的纤维与其它聚合物或非金属材料共混或复合纺丝所得的纤维,所述的其它纤维材料优选聚亚酰胺纤维、聚酯纤维、聚四氟乙烯纤维的一种或
两种以上,所述的其它聚合物优选聚亚酰胺、聚酯、聚四氟乙烯的一种或两种以上,所述的非金属材料优选陶瓷纤维或玄武岩纤维的一种或两种。
所述的纤维材料的形式为通过针刺、水刺技术或者是熔喷法、纺粘法制备的非织造布。
所述的纤维材料厚度为O. l—8.0腿,优选为0.5-6mm;克重为30—1500g/m2,优选为100-1000g/m2 。
以过滤毡重量为基准计,所述的功能催化剂含量为O. l_98wt%,优选为2-80wt呢。
所述的功能性催化剂是由浸渍法、沉淀法、化学沉积、共混法和涂敷法中的一种或多种方法,将具有催化脱硫和/或脱氮反应的活性组分与催化剂载体结合。;
所述的活性组分由贵金属、金属氧化物一种或多种构成;所述的催化剂载体为沸石类、Ti02、 Zr02、 A1203、 Si02、 Ge02、活性碳纤维、活性炭载体、玻璃纤维、陶瓷纤维和多孔支撑材料中的一种或多种,所述的多孔支撑材料是加工成的多孔、板式、蜂窝状或者波纹状的玻璃钢、烧结金属、陶瓷材料中的一种或者两种以上制成。
所述的贵金属为金、银或铂族金属中的一种或几种,所述的铂族金属为钌、铑、钯、锇、铱或铂;
所述的金属氧化物为过渡金属氧化物,所述的过渡金属为Fe、 Cu、 Mn、 Co、 V、Mo、 W或Ce,所述的过渡金属氧化物为一种或多种上述过渡金属的一种或多种氧化物,优选CuO、 Cu20、 V205、 CoO、 Co203、 Mn02、 Mn203、 Mn304、 Fe203、 FeO、 Fe304、 Mo03、 W03、Ce02中的一种或多种。
本发明提供了上述的过滤毡的制备方法,其特征在于,将纤维材料和具有催化脱硫和/或脱氮反应的功能性催化剂复合,然后成毡即得到过滤毡。
其中,所述的纤维材料和具有催化脱硫和/或脱氮反应的功能性催化剂复合方式为在纤维材料的制备过程中纤维材料与催化剂通过粘接或附着的方式进行复合;
或在过滤毡制造过程中将功能催化剂置于纤维材料夹层中;
或将纤维材料与以多孔支撑材料为催化剂载体的功能催化剂通过粘接方式复合。
本发明还提供了上述的过滤毡的应用方法,其特征在于,将烟气通过功能性过滤毡或由其制成的烟气袋式过滤器,烟气中的粉尘通过纤维材料过滤掉,氮氧化物和/或硫氧化物利用功能性催化剂的催化反应脱除,这两个过程可同时或顺序发生。
以下是本发明的详细论述。
针对现有技术现状和存在的问题,本发明所要解决的技术问题是在烟气除尘处理的同时,通过催化反应脱除烟气中的硫氧化物(SOx)和氮氧化物(NOx),提供一种耐高温、抗腐蚀的集除尘、脱硫和/或脱氮一体化的烟气有害成分净化用功能性过滤毡,适用于电厂、炼厂、化工厂的烟气除尘、脱硫和脱硝装置,特别适用于烟气袋式过滤器的制造。该过滤毡由纤维材料和功能性催化剂组成,其工作原理是通过纤维材料过滤掉烟气中的粉尘,利用功能性催化剂的催化反应脱除烟气中的氮氧化物和/或硫氧化物。
为了达到以上目的,纤维材料至少需要一层,以达到除尘的目的。当选择两层以上纤维材料层时,可以选择同一种纤维材料,也可以选择不同的纤维材料进行组合。功能性催化剂可以为单独的一层,以粘接方式、附着或通过湿、热、挤压等物理作用或现有技术其它方式与纤维材料复合,也可以在纤维材料的制备过程中,以粒状、粉末状或其它形式分散在纤维材料中。以下介绍几种优选结构:
1、 过滤毡由二层纤维材料层和一层功能性催化剂层构成,功能性催化剂层置于二层纤维材料层之间,可参见附图图l,这样其中之一纤维材料层可以起过滤除尘作用,另一纤维材料层具有阻挡功能催化剂颗粒穿透的作用,可以使过滤毡具有更高的使用寿命。
2、 过滤毡由二层纤维材料层和功能性催化剂构成,功能性催化剂在纤维材料的制备过程中,以粒状、粉末状或其它形式分散在其中至少一层纤维材料层中,二层纤维材料层作用与结构l中纤维材料层相同,可参见附图图2,这样的优点是催化剂分布均匀,表面积大,催化效率更高。
3、 过滤毡由一层纤维材料层和一层功能性催化剂层构成,可参见附图图4,这
样的优点是结构简单,成本低。
除了以上优选结构外,本领域技术人员也可视情况需要,增加纤维材料层数,或增加功能性催化剂层数,或将功能性催化剂层数根据脱硫脱硝的不同分为两层以至更多层,如其中之一层脱硫,另一层脱硝等等,这些都在本发明的保护范围内。
此外,由于工业烟气温度较高,普通纤维难以承受,因此本发明过滤毡中的纤维材料必须具备耐高温特性,只要具备这一特性,即可用于本发明过滤毡,优选的
纤维材料为:
a、 聚苯硫醚、经过等离子体表面改性的聚苯硫醚、芳纶、玻璃纤维中的一种或
两种以上复合纺丝或混纺所得的纤维,或
b、 将a中的纤维与其它纤维材料的复合纺丝或混纺所得的纤维^或
c、 将a或b中的纤维与其它聚合物或非金属材料共混或复合纺丝所得的纤维,其它纤维材料优选聚亚酰胺纤维、聚酯纤维、聚四氟乙烯纤维的一种或两种以
上,其它聚合物优选聚亚酰胺、聚酯、聚四氟乙烯的一种或两种以上,非金属材料优选陶瓷纤维或玄武岩纤维的一种或两种。
本发明纤维材料包括但不限于以上几种纤维材料。
其中玻璃纤维价格低廉,但室温下的强碱及高温下的中等碱性能够侵蚀玻璃。而且玻璃纤维性脆,在曲挠磨损上的抗性极差,如果有脉冲或清灰剧烈,容易损坏;
芳纶纤维具有超高强度、高模量和耐高温、耐酸耐碱、重量轻等优良性能,其强度是
钢丝的5〜6倍,模量为钢丝或玻璃纤维的2〜3倍,韧性是钢丝的2倍,而重量仅为钢丝的l/5左右,在560度的温度下,不分解,不融化。它具有良好的绝缘性和抗老化性能,具有很长的生命周期,但是价格比较高;聚苯硫醚PPS具有极高的熔点和优异的耐热性。此外其阻燃性、耐化学药品性、尺寸稳定性等也极为出众,是一种高性能纤维,并能抵抗许多酸、碱和氧化剂的化学腐蚀,而且价格适中,因此以性价比而言,优选聚苯硫醚(PPS)。聚苯硫醚可以经过等离子体表面改性,能够改变材料表面的物理结构或化学组分,使材料的性能得以显著改善和提高;此外,可以将以上纤维与其它纤维材料混合,或是将其与其它聚合物或非金属材料共混或复合纺丝,以满足各种不同行业烟气的具体特殊要求,在此毋庸一一赘述。
还可以通过现有的针刺、水刺技术或者熔喷法、纺粘法,将以上纤维材料制备成非织造布,也可以用于本发明。本发明中的纤维材料,厚度可以根据烟气含尘量具体调整, 一般而言,厚度为O. l — 8.0mm,优选O. 5_6腿;克重为30—1500g/m2,优选为100-1000g/m2。
除了纤维材料,本发明的另一组成成分为功能性催化剂,其作用是催化脱除烟气中的氮氧化物和/或硫氧化物。以过滤毡重量为基准计,功能催化剂含量为0.1 —98wt%,优选为2-8(kt%。功能性催化剂是由浸渍法、沉淀法、化学沉积、共混法和涂敷法中的一种或多种方法,将具有催化脱硫和/或脱氮反应的活性组分与催化剂载体结合。
其中,活性组分能够催化脱硫或脱氮反应,或者二者兼有,只要具有这一功能,即可用于本发明。如贵金属、金属氧化物等,也可以是以上几种的混合物。下面简述其中几种,但本发明活性成分包括但不限于以下所述:
贵金属为金、银或铂族金属中的一种或几种,铂族金属包括钌、铑、钯、锇、铱或铂,可用于催化脱硝反应,金属氧化物一般为过渡金属氧化物,过渡金属为Cu、Fe、 Mn、 Co、 V、 Mo、 W、 Ce等等,过渡金属氧化物为一种或多种上述过渡金属的一种或多种氧化物,优选CuO、 Cu20、 V205、 CoO、 Co203、 Mn02、 Mn203、 MnA、 Fe203、 FeO、Fe304、 Mo03、 W03、 &02等中的一种或多种,都具有催化脱硝反应的能力,其中上述贵金属、金属氧化物中一些还兼具催化脱硫功能,如CuO脱硫脱硝的原理如下:
CuO与烟气中的S02、 S03和02反应生成CuS04,方程式为:
2Cu0+2S02+02— 2CuS04
Cu0+S03— CuS。4
而CuO和CuS(X又同时是N0x催化还原的催化剂,在02及还原剂朋3存在下会发生以下脱硝反应:
4NH3 + 4N0 + 02—4N2 + 6H20 2丽3 + NO + N02 — 2N2 + 3H20
当催化剂吸收S02接近饱和时,可利用一定浓度的NaOH溶液浸泡CuS04,生成不 溶性的Cu(OH)2和可溶性的Na2S04,再经水洗涤除去^》04得到01 (OH)2, Cu(OH)2经温度 大于8(TC的烟道气加热,即生成CuO重新使用。
此外,热能动力工程,16(4) :444-446报道了活性炭可用于烟气同时脱硫脱硝; Carbon, 2003(41) : 1079-1085报道了铜炭催化剂、铁炭催化剂、钒炭催化剂均可用 于烟气同时脱除S02、N0以及HC1,并且都具有较高的活性。染料化学学报,33(1) :6-11 报道了钒炭催化剂(V205/AC)用于烟气同时脱硫脱硝,以上几种催化剂均可做为本发 明中的活性组分。
具有催化脱硫和/或脱氮反应的活性组分与催化剂载体结合,即可制备功能性催 化剂。制备方法包括但不限于浸渍法、共混法和涂敷法中的一种或多种方法,催化 剂载体包括但不限于沸石类、Ti02、 Zr02、 A1203、 Si02、 Ge02、活性碳纤维、活性炭 载体、玻璃纤维、陶瓷纤维和多孔支撑材料等,也可以是其中几种的组合,其中多 孔支撑材料是加工成的多孔、板式、蜂窝状或者波纹状的玻璃钢、烧结金属、陶瓷 等材料中的一种或者多种制成。催化剂载体具有较大比表面积,用于支持和固定活 性组分,可使活性组分高度分散在载体表面上,从而提高单位质量活性组分的催化效 率。
将纤维材料与功能性催化剂复合,然后成毡,即可得本发明烟气有害成分净化 用功能性过滤毡。复合方式可以是在纤维材料的制备过程中纤维材料与催化剂通过 粘接或附着的方式进行复合(如说明书附图图2即是其中一种体现);或在过滤毡制 造过程中将功能催化剂置于纤维材料夹层中(如图l即是其中一种体现);或将纤维 材料与以多孔支撑材料为催化剂载体的功能催化剂通过粘接方式复合(如图4即是其 中一种体现)。
本发明还提供了上述烟气有害成分净化用功能性过滤毡的应用方法,将烟气通 过功能性过滤毡或由其制成的烟气袋式过滤器,烟气中的粉尘通过纤维材料过滤掉, 功能性催化剂催化发生脱硝和/或脱硫反应,除去氮氧化物和/或硫氧化物,根据过 滤毡结构的不同,这两个过程可同时或顺序发生,但是总之,烟气通过功能性过滤 毡或由其制成的烟气袋式过滤器后,粉尘、氮氧化物和/或硫氧化物会被一步除去,
10净化后的清洁气体进入后续处理系统。处理工序比较简单。
本发明的有益效果在于,提供了一种是集除尘、脱硫和/或脱氮一体化的烟气有 害成分净化用功能性过滤毡,以之处理烟气,可以简化了烟气净化工序,提高处理 效率,适用于电厂、炼厂、化工厂的烟气除尘、脱硫和脱硝装置,特别适用于制造 烟气袋式过滤器,可以有效地节约费用,非常适合对现有的烟气除尘装置进行改造。
附图说明
图l是本发明中的功能性过滤毡的一种结构示意图,实施例l。 图2是本发明中的功能性过滤毡的一种结构示意图,实施例2、 3、 4、 5、 6。 图3是本发明中的纤维材料与功能性催化剂颗粒的一种复合方式的示意图,实施例2。
图4是本发明中的功能性过滤毡的一种结构示意图,实施例7、 8、 9。 具体实施方式
以下是本发明实施的几种具体方式,但本发明不限于下述实施例,对于本领域 一般技术人员而言,在不背离本发明原理的前提下对它所做的任何显而易见的改动, 都属于本发明的构思和所附权利要求的保护范围。
实施例l
如图l的材料截面示意图所示,功能性过滤毡结构自表向里依次是:PPS纤维层1、
功能性催化剂层2、 PPS纤维层3, 4是待过烟气流动方向。过滤毡可采用现有技术如 聚合物挤压成网法制备。PPS聚合物经过熔喷纺丝后成一层松散的纤维层,将催化剂 颗粒均匀喷溅在这层松散纤维层上形成一层具有一定厚度的催化剂层,在其上盖 一层松散的PPS纤维层,经碾压处理形成PPS纤维网,再经针刺处理加固过滤毡的整 体结构。PPS纤维层l和PPS纤维层3厚度都为0.8mm,克重为250g/m2。功能性催化剂层 2由贵金属、金属氧化物中的一种或多种负载于沸石类、Ti02、 Zr02、 A1203、 Si02、 Ge02、 活性碳纤维、活性炭载体、玻纤维、陶瓷纤维上的一种或多种制成。催化剂含量 以过滤毡重量为基准计算为50wty。。烟气在80。C温度下,通过PPS纤维层1、功能性催 化剂层2,依次发生除尘、脱硫和/或脱硝反应。PPS纤维层3具有阻挡功能催化剂颗 粒穿透的作用。净化后的清洁气体进入后续处理系统。实施例2
如图2的材料截面示意图所示,功能性过滤毡结构自表向里依次是:PPS纤维复 合层l、 PPS纤维层3, PPS纤维复合层1是由PPS纤维与功能催化剂2复合而成,4是待 过烟气流动方向。PPS聚合物经过加温熔化,经挤压熔喷纺丝,在聚合物纤维冷却成 纤和铺展的同时,将催化剂颗粒均匀喷溅到聚合物纤维上,并保证催化剂颗粒分散 均匀不聚集成团。冷却成纤后在其上覆盖一层松散的PPS纤维层,经碾压处理形成PPS 纤维网,再经针刺处理加固过滤毡的整体结构。PPS纤维复合层l厚度为2.5mm,克重 为850g/m2 ,PPS纤维层3厚度为lmm,克重为300g/m2。功能性催化剂2由贵金属、金属 氧化物中的一种或多种负载于沸石类、Ti02、 Zr02、 A1A、 Si02、 Ge02、活性碳纤维、 活性炭载体、玻璃纤维、陶瓷纤维上的一种或多种制成。功能性催化剂含量以过滤 毡重量为基准计算为15wt。/。。烟气在190。C温度下,通过PPS纤维复合层1时,同时发 生烟气的除尘和脱硫和/或脱硝反应。PPS纤维层3具有阻挡功能催化剂颗粒穿透的作 用。净化后的清洁气体进入后续处理系统。
如图3是PPS纤维与功能催化剂颗粒结合的示意图,功能催化剂粒子l以胶粘或附 着的方式与PPS纤维2复合。
实施例3
如图2的材料截面示意图所示,功能性过滤毡结构自表向里依次是:PPS纤维复 合层l、 PPS纤维层3。 PPS纤维复合层1和PPS纤维层中所使用的PPS纤维是通过等离子 体表面改性处理的改性PPS纤维,过滤毡的制备方法如实施例2,功能性催化剂含量 以过滤毡重量为基准计算为O. 5wt%。其它的过滤毡结构参数及其烟气净化方法与实 施例2相同。
实施例4
如图2的材料截面示意图所示,功能性过滤毡结构自表向里依次是:PPS纤维复 合层l、 PPS纤维层3。 PPS纤维复合层1中所使用的PPS纤维是通过PPS与锦抡PA共混改 性后经纺丝制得的改性PPS纤维,克重为770g/m2。过滤毡的制备方法如实施例2,功 能性催化剂含量以过滤毡重量为基准计算为40wty。。其它的过滤毡结构参数及其烟气 净化方法与实施例2相同。
实施例5
如图2的材料截面示意图所示,功能性过滤毡结构自表向里依次是:纤维复合层1、纤维层3。纤维复合层1所使用的纤维是由PPS与玻璃纤维混合加工而成,克重为 1000g/m2。过滤毡的制备方法、其它的过滤毡结构参数及其烟气净化方法与实施例2 相同。
实施例6
如图2的材料截面示意图所示,功能性过滤毡结构自表向里依次是:PPS纤维复 合层l、 PPS纤维层3。 PPS纤维复合层1和PPS纤维层中所使用的PPS纤维是通过纺粘法 制得。功能性催化剂含量以过滤毡重量为基准计算为2wt。/。。 PPS非织造布,过滤毡的 制备方法、其它的过滤毡结构参数及其烟气净化方法与实施例2相同。 实施例7
如图4的材料截面示意图所示,功能性过滤毡结构自表向里依次是:PPS纤维层 1、功能性催化剂层2, PPS纤维层1和功能性催化剂层2以粘接方式复合,3是待过烟 气流动方向。PPS纤维层l厚度为1.6mra,克重为450g/m2。功能性催化剂层2由贵金属、 金属氧化物中的一种或多种负载于沸石类、Ti02、 Zr02、 A1203、 Si02、 Ge02、活性碳 纤维、活性炭载体、玻璃纤维、陶瓷纤维上的一种或多种构成,并涂敷在多孔支撑 材料上制得。功能性催化剂含量以过滤毡重量为基准计算为80wty。。烟气在20(TC温 度下,通过PPS纤维层1、功能性催化剂层2,依次发生除尘、脱硫和/或脱硝反应。 净化后的清洁气体进入后续处理系统。 实施例8
如图4的材料截面示意图所示,功能性过滤毡结构自表向里依次是:PPS纤维层1、 功能性催化剂层2, PPS纤维层l厚度为O. lmra,克重为30g/m2。功能性催化剂含量以过 滤毡重量为基准计算为O. lwt%。其它的过滤毡结构参数及其烟气净化方法与实施例7 相同。
实施例9
如图4的材料截面示意图所示,功能性过滤毡结构自表向里依次是:PPS纤维层1、 功能性催化剂层2, PPS纤维层l厚度为8.0mm,克重为1500g/m2。功能性催化剂含量以 过滤毡重量为基准计算为98w"/。。其它的过滤毡结构参数及其烟气净化方法与实施例 7相同。
实施例IO
如图4的材料截面示意图所示,功能性过滤毡结构自表向里依次是:PPS纤维层1、 功能性催化剂层2, PPS纤维层l厚度为0.5mra,克重为100g/m2。催化剂含量以过滤毡重量为基准计算为65wty。,其它的过滤毡结构参数及其烟气净化方法与实施例7相同。 实施例ll
如图4的材料截面示意图所示,功能性过滤毡结构自表向里依次是:PPS纤维层1、
功能性催化剂层2, PPS纤维层l厚度为6.0mm,克重为1000g/m2。催化剂含量以过滤毡 重量为基准计算为53wty。,其它的过滤毡结构参数及其烟气净化方法与实施例7相同。 比较例l:
本比较例的目的在于研究本发明和专利CN2669958Y除尘和脱硫脱硝效果。 对于含有S0^500ppm、 NOx^000ppm的烟气,NH3浓度为1500卯m,烟气温度200。C, 空速40000h—'下,将实施例l一ll的产品用于除尘脱硫和/或脱硝,过滤毡除尘后的烟 尘排放浓度为小于50mg/m3,如果采用的是具有同时脱硫脱硝作用的催化剂,脱硫脱硝 效果为:脱硫率为80_92%,脱硝率为80 — 89%;如果采用的是只具有脱硫或脱硝功 能的催化剂,则脱硫或脱硝率可达85 — 93%.
在同样的烟气条件和空速下,将专利CN2669958Y的实施例1一3制得的过滤毡用 于除尘脱硫,过滤毡除尘后的烟尘排放浓度为小于60mg/m3,脱硫率为16_35%。
Claims (15)
1、一种烟气有害成分净化用功能性过滤毡,其特征在于,所述的过滤毡由纤维材料和具有催化脱硫和/或脱氮反应的功能性催化剂组成。
2、 根据权利要求l所述的过滤毡,其特征在于,所述功能性催化剂以粘接、附着或 通过湿、热、挤压等物理作用或化学反应与纤维材料复合。
3、 根据权利要求l所述的过滤毡,其特征在于,所述的纤维材料至少为一层,所述 的功能性催化剂为单独的一层或分散在纤维材料中。
4、 根据权利要求l所述的过滤毡,其特征在于,所述的过滤毡由两层纤维材料层和 一层功能性催化剂层构成,功能性催化剂层置于两层纤维材料层之间; 或所述的过滤毡由两层纤维材料层和功能性催化剂构成,功能性催化剂分散在纤维 材料层中;或所述的过滤毡由一层纤维材料层和一层功能性催化剂层构成。
5、 根据权利要求1 —4任意一项所述的过滤毡,其特征在于,所述的纤维材料具备耐 高温特性。
6、 根据权利要求5所述的过滤毡,其特征在于,所述的纤维材料为a、 聚苯硫醚、经过等离子体表面改性的聚苯硫醚、芳纶、玻璃纤维中的一种或两种 以上复合纺丝或混纺所得的纤维;或b、 将a中的纤维与其它纤维材料复合纺丝或混纺所得的纤维;或c、 将a或b中的纤维与其它聚合物或非金属材料共混或复合纺丝所得的纤维; 所述的其它纤维材料优选聚亚酰胺纤维、聚酯纤维、聚四氟乙烯纤维的一种或两种 以上,所述的其它聚合物优选聚亚酰胺、聚酯、聚四氟乙烯的一种或两种以上,所 述的非金属材料优选陶瓷纤维或玄武岩纤维的一种或两种。
7、 根据权利要求1一6任意一项所述的过滤毡,其特征在于,所述的纤维材料的形式 为通过针剌、水刺技术或者是熔喷法、纺粘法制备的非织造布。
8、 根据权利要求1一7任意一项所述的过滤毡,其特征在于,所述的纤维材料厚度为 0. 1 —8. 0腿,优选为O. 5-6mm;克重为30—1500g/m2,优选为100-1000g/m2 。
9、 根据权利要求1-8所述的过滤毡,其特征在于,以过滤毡重量为基准计,所述的 功能催化剂含量为O. l_98wt%,优选为2-80wt0/0。
10、 根据权利要求1一4任意一项或权利要求8所述的过滤毡,其特征在于,所述的功 能性催化剂是由浸渍法、沉淀法、化学沉积、共混法和涂敷法中的一种或多种方法, 将具有催化脱硫和/或脱氮反应的活性组分与催化剂载体结合。
11、 根据权利要求10所述的过滤毡,其特征在于,所述的活性组分由贵金属、金属 氧化物一种或多种构成;所述的催化剂载体为沸石类、Ti02、 Zr02、 A1203、 Si02、 Ge02、活性碳纤维、活性炭 载体、玻璃纤维、陶瓷纤维和多孔支撑材料中的一种或多种;所述的多孔支撑材料是加工成的多孔、板式、蜂窝状或者波纹状的玻璃钢、烧结金 属、陶瓷材料中的一种或者两种以上制成。
12、 根据权利要求ll所述的过滤毡,其特征在于,所述的贵金属为金、银或铂族金 属中的一种或几种,所述的铂族金属为钌、铑、钯、锇、铱或铂; 所述的金属氧化物为过渡金属氧化物,所述的过渡金属为Fe、 Cu、 Mn、 Co、 V、 Mo、 W或Ce,所述的过渡金属氧化物为一种或多种上述过渡金属的一种或多种氧化物; 优选CuO、 Cu20、 VA、 CoO、 Co203、 Mn02、 Mn203、 Mn304、 Fe203、 Fe0、 Fe:A、 MoO:,、 W03、 Ce02中的一种或多种。
13、 权利要求1一12任意一项所述的过滤毡的制备方法,其特征在于,将纤维材料和 具有催化脱硫和/或脱氮反应的功能性催化剂复合,然后成毡即得到过滤毡。
14、 根据权利要求13所述的制备方法,其特征在于,所述的纤维材料和具有催化脱 硫和/或脱氮反应的功能性催化剂复合方式为在纤维材料的制备过程中纤维材料与 催化剂通过粘接或附着的方式进行复合; 或在过滤毡制造过程中将功能催化剂置于纤维材料夹层中;或将纤维材料与以多孔支撑材料为催化剂载体的功能催化剂通过粘接方式复合。
15、 权利要求1 —14任意一项所述的过滤毡的应用方法,其特征在于,将烟气通过功 能性过滤毡或由其制成的烟气袋式过滤器,烟气中的粉尘通过纤维材料过滤掉,氮 氧化物和/或硫氧化物利用功能性催化剂的催化反应脱除,这两个过程可同时或顺序 发生。
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